EP1798272B1 - Manufacturing process for an optical article and article so obtained - Google Patents
Manufacturing process for an optical article and article so obtained Download PDFInfo
- Publication number
- EP1798272B1 EP1798272B1 EP06291705A EP06291705A EP1798272B1 EP 1798272 B1 EP1798272 B1 EP 1798272B1 EP 06291705 A EP06291705 A EP 06291705A EP 06291705 A EP06291705 A EP 06291705A EP 1798272 B1 EP1798272 B1 EP 1798272B1
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- EP
- European Patent Office
- Prior art keywords
- coating
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- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 230000003287 optical effect Effects 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 81
- 239000011248 coating agent Substances 0.000 claims abstract description 69
- 239000006096 absorbing agent Substances 0.000 claims abstract description 40
- 239000000243 solution Substances 0.000 claims abstract description 40
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 229920000106 Liquid crystal polymer Polymers 0.000 claims abstract description 20
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims abstract description 20
- 238000005213 imbibition Methods 0.000 claims abstract description 20
- 238000007654 immersion Methods 0.000 claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 11
- 238000001782 photodegradation Methods 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 33
- 238000005299 abrasion Methods 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 13
- 239000004973 liquid crystal related substance Substances 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 10
- 229920000058 polyacrylate Polymers 0.000 claims description 8
- 229920006243 acrylic copolymer Polymers 0.000 claims description 5
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical group OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-UHFFFAOYSA-N 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- -1 poly(ethylene terephthalate) Polymers 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 4
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical group CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 150000001565 benzotriazoles Chemical group 0.000 claims description 3
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 claims description 2
- JHQVCQDWGSXTFE-UHFFFAOYSA-N 2-(2-prop-2-enoxycarbonyloxyethoxy)ethyl prop-2-enyl carbonate Chemical compound C=CCOC(=O)OCCOCCOC(=O)OCC=C JHQVCQDWGSXTFE-UHFFFAOYSA-N 0.000 claims description 2
- PQJZHMCWDKOPQG-UHFFFAOYSA-N 2-anilino-2-oxoacetic acid Chemical class OC(=O)C(=O)NC1=CC=CC=C1 PQJZHMCWDKOPQG-UHFFFAOYSA-N 0.000 claims description 2
- ZCILGMFPJBRCNO-UHFFFAOYSA-N 4-phenyl-2H-benzotriazol-5-ol Chemical compound OC1=CC=C2NN=NC2=C1C1=CC=CC=C1 ZCILGMFPJBRCNO-UHFFFAOYSA-N 0.000 claims description 2
- NJCDRURWJZAMBM-UHFFFAOYSA-N 6-phenyl-1h-1,3,5-triazin-2-one Chemical compound OC1=NC=NC(C=2C=CC=CC=2)=N1 NJCDRURWJZAMBM-UHFFFAOYSA-N 0.000 claims description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 230000002209 hydrophobic effect Effects 0.000 claims description 2
- 229920000636 poly(norbornene) polymer Polymers 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims description 2
- 150000003918 triazines Chemical class 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims 1
- QEMSHZOGUJXBQA-UHFFFAOYSA-N sulfanyl carbamate Chemical compound NC(=O)OS QEMSHZOGUJXBQA-UHFFFAOYSA-N 0.000 claims 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 50
- 239000000975 dye Substances 0.000 description 28
- 239000000203 mixture Substances 0.000 description 10
- JLZIIHMTTRXXIN-UHFFFAOYSA-N 2-(2-hydroxy-4-methoxybenzoyl)benzoic acid Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1C(O)=O JLZIIHMTTRXXIN-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- FMRHJJZUHUTGKE-UHFFFAOYSA-N Ethylhexyl salicylate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1O FMRHJJZUHUTGKE-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 5
- 239000006117 anti-reflective coating Substances 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 239000004814 polyurethane Substances 0.000 description 3
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- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 2
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- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 2
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- 238000002791 soaking Methods 0.000 description 2
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- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical group O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- CEUQYYYUSUCFKP-UHFFFAOYSA-N 2,3-bis(2-sulfanylethylsulfanyl)propane-1-thiol Chemical compound SCCSCC(CS)SCCS CEUQYYYUSUCFKP-UHFFFAOYSA-N 0.000 description 1
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 241001639412 Verres Species 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 125000000332 coumarinyl group Chemical class O1C(=O)C(=CC2=CC=CC=C12)* 0.000 description 1
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- 238000000151 deposition Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 206010014801 endophthalmitis Diseases 0.000 description 1
- 230000004313 glare Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000001659 ion-beam spectroscopy Methods 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
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- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- NIEHEMAZEULEKB-UHFFFAOYSA-N ortho-ethylanisole Natural products CCC1=CC=CC=C1OC NIEHEMAZEULEKB-UHFFFAOYSA-N 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 150000002979 perylenes Chemical class 0.000 description 1
- 150000002991 phenoxazines Chemical class 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 229920002578 polythiourethane polymer Polymers 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003553 thiiranes Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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- 238000002604 ultrasonography Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
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- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/60—Pleochroic dyes
Definitions
- the invention relates to a method of manufacturing a polarized optical article, in particular a polarized ophthalmic lens, comprising a step of imbibing the article with a UV absorber under specified conditions. It also relates to a polarized optical article, in particular capable of being obtained according to the preceding method.
- WO 02/059054 discloses a process for impregnating a thin layer made of a latex polymer matrix (in particular optionally crosslinked polyurethane) deposited on an optical glass.
- the impregnating solution is applied by centrifugation to the thin layer and contains an additive such as a dye.
- Such a method makes it possible in particular to obtain an ophthalmic lens comprising a tinted coating.
- Requirement JP11-052101 discloses a method of impregnating the substrate of a lens with a solution containing a UV absorber and a dye for compensating for lens coloration induced by said UV absorber.
- the impregnation process is carried out at 90 Ā° C for 15 minutes.
- the demand JP09-145901 discloses a method of impregnating a plastic lens substrate, using two successive solutions containing, for the first, a UV absorber (intended to protect the eye and the lens material against UV) associated with a staining assistant and optionally a dispersant, and, for the second, a dye.
- EP 1 593 990 A1 discloses a polarized ophthalmic article comprising a substrate and a trilayer coating comprising a first photo-orientation layer (ie photoalignment) based on a polyacrylate or polyimide, a second layer of liquid crystal polymers comprising a dichroic dye, and a layer of protection.
- a first photo-orientation layer ie photoalignment
- a second layer of liquid crystal polymers comprising a dichroic dye
- the inventions described in the aforementioned applications made it possible to introduce UV absorbers in optical articles, and more particularly in the substrate constituting said article. However, they are not always adapted to protect dyes sensitive to photodegradation due to ultraviolet radiation.
- dyes sensitive to such reactions mention may be made of dichroic or photochromic dyes which contain, in particular, aromatic units, some of which may be sensitive to UV radiation.
- dichroic dyes are especially used in combination with liquid crystals to provide a property of polarization of the object that includes them, such as for example polarized ophthalmic lenses.
- Polarized lenses have experienced a great development in recent years, insofar as they greatly improve the comfort of vision by limiting the glare caused by reflections from reflective surface such as water. The result is a better perception of contrasts and depth.
- a polarization-functional bilayer coating containing a layer of liquid crystal polymer (LCP) containing dichroic dyes, and a "linear photopolymer (LPP)" layer to give the substrate comprising a function thereof.
- LCP liquid crystal polymer
- LPP linear photopolymer
- coatings are used in display screens, but can also be used with optical articles ( US 5,602,661 , US 2005/0151926 ; EP 1 593 990 ).
- the LPP layer consists of a material which, once polymerized under the effect of linearly polarized UV, will be structured and allow the organization of liquid crystal molecules and the alignment of dichroic dyes in a particular direction .
- ophthalmic lenses having a relative relative transmission factor in the visible range (T v ) of between 80% and 6%, associated with a contrast ratio which is greater than that generally observed for polarizing lenses obtained by bonding or rolling a polarizing film, and which commonly reaches values greater than 100.
- the coating of linear photopolymer type (LPP) and liquid crystal polymer type (LCP) can be deposited by centrifugation (spin) on an organic substrate. This process is fully integrated into the production lines and allows in particular to obtain ophthalmic lens whose lens is constituted by any type of substrate.
- the dichroic dyes present in these polarizing bilayer coatings are sensitive to UV, which generally results in a loss of polarizing performance, in particular by a drop in the contrast ratio (CR), an increase in transmission (Tv %) and a change in color ( ā E), which is not acceptable for a polarizing lens that must be usable under conditions of strong sunlight.
- CR contrast ratio
- Tv increase in transmission
- ā E change in color
- the present invention also relates to a polarized optical article that can be obtained according to the method defined above.
- lower alcohol means a mono-alcohol containing 2 to 4 carbon atoms such as ethanol or isopropanol and in particular isopropanol.
- the substrate of the optical article in particular of the ophthalmic lens, may be of mineral or organic type. As an indication but not limited to, there may be mentioned as an organic substrate that can be used in the context of the invention substrates conventionally used in optics and ophthalmia.
- substrates of the polycarbonate type are suitable; polyamide; polyimides; polysulfones; copolymers of poly (ethylene terephthalate) and polycarbonate; polyolefins, especially polynorbornenes; polymers and copolymers of diethylene glycol bis (allyl carbonate); (meth) acrylic polymers and copolymers, especially polymers and (meth) acrylic copolymers derived from bisphenol-A; thio (meth) acrylic polymers and copolymers; urethane and thiourethane polymers and copolymers; epoxy polymers and copolymers and episulfide polymers and copolymers.
- the invention is particularly well suited for ophthalmic lenses whose substrate is a poly (thio) urethane.
- the first step of the process according to the invention comprises the application of the bilayer coating.
- This coating comprises a layer of photopolymer (s) or photo-orientable polymer (s) deposited on the substrate and on which the layer of polymer (s) liquid crystal is deposited.
- Liquid crystal solutions and / or linear photopolymer can be applied by spin coating, dipping or spraying. Centrifugal application is preferred in the present invention.
- the linear photopolymer layer may thus consist of acrylic or methacrylic polymers, dendrimers or polyimides, having reactive groups of the cinnamic acid derivative type, chalcones or coumarins. These materials may be carried in a solvent such as acetone, dichloromethane, or in a solvent mixture such as methyl ethyl ketone / cyclopentanone.
- the photo-polymerization step can be carried out after a step possible drying of the solution, and be performed by exposure to polarized UV light.
- the liquid crystal polymers and the dichroic dyes may be carried in a solvent such as cyclohexanone or in mixtures such as anisole / acetone, anisole / ethyl acetate or anisole / cyclopentanone.
- the coating consisting of the mixture of liquid crystals and dichroic dyes may be subjected (possibly after a drying step) to UV irradiation to allow its polymerization.
- the dichroic dyes may or may not be polymerizable, preferably polymerizable.
- Preferred dichroic dyes have a high dichroic ratio, a high extinction coefficient, and good solubility. It can be azo dyes, perylenes, anthraquinones or phenoxazines. Azo and anthraquinone dyes are preferred because they are particularly well compatible with the liquid crystal polymers used in the context of the invention.
- this polarizing system although having a low glass transition temperature once crosslinked (Tg ā 20 Ā° C), could be imbibed by a UV absorber solution at a temperature above 80 Ā° C without affecting noticeably the orientation of the dichroic dyes. This is easily demonstrated by contrast ratio measurements before and after the imbibition step. It is thus possible, with this system, to use high imbibition temperatures, of the order of 95 Ā° C, which allow a rapid diffusion of the UV absorber in the polarizing system and thus obtaining a UV cut close to 380 nm after 30 seconds of imbibition.
- the aforementioned polarizing system prevents the desorption of the UV absorber during the subsequent treatment of the optical article, for example when applying a double-layer anti-abrasion coating in the presence of soda and alcohol, and thus confers a good chemical resistance to the article.
- the coating thus obtained generally has a thickness of 1 to 20 microns (micrometer), and preferably 3 to 8 microns.
- the second step of the process according to the invention comprises the impregnation of at least one UV absorber in the polarized optical article.
- Non-limiting examples of UV absorbers used in the process according to the invention are chosen from benzotriazoles, in particular hydroxyphenylbenzotriazole; triazines such as hydroxyphenyl-S-triazine; hydroxybenzophenones; and oxalic anilides.
- the UV absorber is preferably selected from the absorbers of the family of benzophenones and benzotriazoles. These absorbers are particularly suitable for absorbing UV at the wavelengths generating the most photodegradation of the UV-sensitive dyes, in the range of interest within the scope of the invention.
- the preferably selected UV absorbers are the CYASORB Ā® UV 24, Cyasorb Ā® UV-1164L, Cyasorb Ā® UV-1164 A, CYASORB Ā® UV-2337, Cyasorb Ā® UV-531, Cyasorb Ā® UV-5411 and CYASORB Ā® UV-9, all commercially available from CYTEC.
- Other UV absorbers used in the present invention are Uvinul Ā® 300, Uvinul Ā® 3008, Uvinul Ā® 3040, UVINUL Ā® 3048, UVINUL Ā® 3049 and UVINUL Ā® 3050, available from BASF.
- UV absorbers are TINUVIN Ā® 1130, TINUVIN Ā® 292, TINUVIN Ā® 5151, TINUVIN Ā® 99-2, TINUVIN Ā® 384-2, TINUVIN Ā® 3050, TINUVIN Ā® 5055 and TINUVIN Ā® 5060 available from CIBA.
- Further examples of UV absorbers are SANDWOR Ā® 3041, the Sanduvor Ā® 3051, Sanduvor 3063 Ā®, 3070 Ā® Sanduvor and Sanduvor Ā® 3225 available from Clariant.
- the CYASORB UV Ā® 24 is particularly preferred in the present invention; it is 2,2'-dihydroxy-4-methoxybenzophenone.
- a dispersing agent such as dodecylbenzenesulphonic acid is introduced. This dispersing agent makes it possible to avoid the formation of aggregate of the UV absorber within said impregnation solution.
- the amount of UV absorber in the impregnating solution must be large enough to allow rapid impregnation of the polarizing coating present on the optical article, and low enough not to lead to the formation of aggregate within the optical article. impregnation solution.
- the rapid impregnation of the optical article is an important condition. Indeed, if the immersion time of the optical article is too long (greater than 2 minutes) there is a detachment of the coating of the substrate surface constituting the optical article.
- the method according to the invention makes it possible to introduce the UV absorber at least partially into the polarizing bilayer coating.
- the immersion time of the optical article in the immersion bath is between 10 seconds and 2 minutes. This is an optimal time to obtain an optical article having optimized photodegradation resistance, while retaining good cosmetic properties, a contrast ratio similar to that obtained for a polarized article that has not undergone the process. impregnation, as well as good adhesion properties on the optical article of both said bilayer and any coatings that can be deposited on this bilayer.
- An immersion time of about 30 seconds is particularly preferred.
- the temperature of the immersion bath which ranges from 80 Ā° C to 99 Ā° C, is preferably between 90 Ā° C and 96 Ā° C, more preferably equal to 94 Ā° C.
- the immersion bath is an aqueous solution.
- the optical article manufactured according to the invention may comprise one or more coatings such as for example: an anti-abrasion coating, for example of the bilayer type, optionally applied to a primer layer; a tinted coating; an oxygen barrier coating; an anti-reflective coating, for example four layers; a hydrophobic and oleophobic antifouling coating; or an antistatic coating.
- an anti-abrasion coating for example of the bilayer type, optionally applied to a primer layer
- a tinted coating an oxygen barrier coating
- an anti-reflective coating for example four layers
- a hydrophobic and oleophobic antifouling coating for example four layers
- an antistatic coating such as for example: an anti-abrasion coating, for example of the bilayer type, optionally applied to a primer layer; a tinted coating; an oxygen barrier coating; an anti-reflective coating, for example four layers; a hydrophobic and oleophobic antifouling coating; or an antistatic coating.
- the primer layer when used, improves the impact strength of the article on which it is deposited and also the anchoring of the abrasion-resistant layer.
- the primer layer may be any primer layer conventionally used in the optical field and in particular ophthalmic.
- these primers, in particular the anti-shock primers are coatings based on (meth) acrylic polymers, polyurethanes, polyesters, or based on epoxy / (meth) acrylate copolymers.
- the anti-abrasion coating may be any anti-abrasion coating conventionally used in the field of optics and in particular ophthalmic optics.
- an anti-abrasion coating is a coating that improves the abrasion resistance of the finished optical article compared to the same article without the abrasion-resistant coating.
- Preferred anti-abrasion coatings are those obtained by curing a composition including one or more epoxyalkoxysilanes or a hydrolyzate thereof, silica and a curing catalyst. Examples of such compositions are described in the international application WO 94/10230 and patents US 4,211,823 , US 5,015,523 , as well as in the European patent EP 614 957 and in particular in Example 3 of this patent. It is thus possible to use an anti-abrasion coating made from compounds marketed by ULTRA OPTICS under the reference UV-NV.
- the oxygen barrier coating generally comprises either a dense metal oxide layer, a non-dense metal oxide layer, or a system comprising a stack of 1 to 4 different metal oxide layers.
- a polarizing coating is applied to a high index lens whose substrate is a polythiourethane.
- the preferred polythiol is 1,2-bis (2'-mercaptoethylthio) -3-mercaptopropane (MDO).
- MDO 1,2-bis (2'-mercaptoethylthio) -3-mercaptopropane
- the preferred isocyanate is m-xylene diisocyanate. The procedure is as described in the patent application EP 1 593 990 .
- the lens is washed in a 5% sodium hydroxide solution in an ultrasound bath at 55 Ā° C. It is then soaked in water and then in deionized water (optionally in isopropanol).
- a 2% by weight solution comprising an acrylic polymer having cinnamic acid functions is prepared in a mixture of methyl ethyl ketone and cyclopentanone (10: 1). This solution is deposited by centrifugation (spin) on the substrate of the lens. The rotation speed is 500 rpm for 3 seconds, then 2500 rpm for 20 seconds.
- the solvent is evaporated by heating in an oven at 100 Ā° C for 20 minutes. This layer is irradiated under a UV polarizer at a dose of 100 mJ / cm 2 .
- a solution containing liquid crystal molecules and dichroic dyes sensitive to ultraviolet degradation is prepared in cyclohexanone.
- the solid part contained in this solution is typically 40% by weight.
- the amount of dichroic dye is about 10% by weight.
- the LCP layer is dried for 10 minutes at a temperature of 87 Ā° C. After evaporation of the solvents, this layer is crosslinked under a nitrogen atmosphere by irradiation in the presence of a UV source at a dose of 30 J / cm 2 .
- the lens is immersed for 30 seconds in the bath prepared as described above, before being rinsed in an isopropanol bath in order to remove the acid and UV absorber residues present on the surface of the lens.
- the UV cutoff (wavelength for which the transmission becomes less than 1%) of the polarized coating alone is equal to 380 nm. This UV cutoff is measured using a spectrometer on a polarized coating deposited on a mineral biplane.
- the figure 3 shows the UV breaks obtained for zero wetting times, 10 seconds and 30 seconds.
- the UV cutoff, initially 330 nm becomes equal to 345 nm after 10 seconds of imbibition then equal to 385 nm after 30 seconds.
- a traditional four-layer anti-reflective coating comprising alternating zirconium oxide and silicon oxide layers is then applied until a total stacking thickness of 200 nm is achieved.
- the different layers are made in a BAK machine, rotating under a high vacuum of 2 x 10 -5 .
- Example 1 Lens comprising a bilayer-coated bilayer, an anti-abrasion bilayer coating and a four-layer anti-reflective coating
- Example 2 Lens comprising a bi-layered, bilayer-impregnated coating, an anti-abrasion bilayer coating and a four-layer anti-reflective coating
- the figures 1 and 2 illustrate the variations of the values of Tv and the hue ( ā E).
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Abstract
Description
L'invention concerne un procĆ©dĆ© de fabrication d'un article optique polarisĆ©, en particulier d'une lentille ophtalmique polarisĆ©e, comprenant une Ć©tape d'imbibition de l'article par un absorbeur UV dans des conditions dĆ©terminĆ©es. Elle concerne Ć©galement un article optique polarisĆ©, en particulier susceptible d'ĆŖtre obtenu selon le procĆ©dĆ© prĆ©cĆ©dent.The invention relates to a method of manufacturing a polarized optical article, in particular a polarized ophthalmic lens, comprising a step of imbibing the article with a UV absorber under specified conditions. It also relates to a polarized optical article, in particular capable of being obtained according to the preceding method.
Il est connu d'introduire des substances telles que des colorants ou des absorbeurs UV dans des lentilles optiques par un procƩdƩ dit d'imprƩgnation ou d'imbibition.It is known to introduce substances such as dyes or UV absorbers in optical lenses by a so-called impregnation or imbibition process.
Ainsi, la demande
La demande
Enfin, la demande
Les inventions dĆ©crites dans les demandes citĆ©es prĆ©cĆ©demment ont permis d'introduire des absorbeurs UV dans des articles optiques, et plus particuliĆØrement dans le substrat constitutif dudit article. NĆ©anmoins elles ne sont pas toujours adaptĆ©es pour protĆ©ger des colorants sensibles Ć la photodĆ©gradation due aux rayonnements ultraviolets. Parmi les colorants sensibles Ć de telles rĆ©actions ont peut citer les colorants dichroĆÆques ou photochromiques qui contiennent notamment des motifs aromatiques dont certains peuvent ĆŖtre sensibles aux rayonnements UV. De tels colorants dichroĆÆques sont notamment utilisĆ©s en combinaison avec des cristaux liquides afin d'apporter une propriĆ©tĆ© de polarisation de l'objet qui les comprend, tel que par exemple les lentilles ophtalmiques polarisĆ©es.The inventions described in the aforementioned applications made it possible to introduce UV absorbers in optical articles, and more particularly in the substrate constituting said article. However, they are not always adapted to protect dyes sensitive to photodegradation due to ultraviolet radiation. Among the dyes sensitive to such reactions, mention may be made of dichroic or photochromic dyes which contain, in particular, aromatic units, some of which may be sensitive to UV radiation. Such dichroic dyes are especially used in combination with liquid crystals to provide a property of polarization of the object that includes them, such as for example polarized ophthalmic lenses.
Les lentilles polarisĆ©es ont connu un grand dĆ©veloppement ces derniĆØres annĆ©es, dans la mesure oĆ¹ elles amĆ©liorent grandement le confort de vision en limitant l'Ć©blouissement provoquĆ© par les reflets provenant de surface rĆ©flĆ©chissante telle que l'eau notamment. Il en rĆ©sulte une meilleure perception des contrastes et de la profondeur.Polarized lenses have experienced a great development in recent years, insofar as they greatly improve the comfort of vision by limiting the glare caused by reflections from reflective surface such as water. The result is a better perception of contrasts and depth.
En particulier, il est connu d'utiliser un revĆŖtement bicouche Ć fonction polarisante contenant une couche de polymĆØre Ć cristaux liquides (LCP) renfermant des colorants dichroĆÆques, et une couche de "photopolymĆØre linĆ©aire (LPP)" pour confĆ©rer au substrat le comprenant une fonction polarisante. De tels revĆŖtements sont notamment utilisĆ©s dans des Ć©crans d'affichage, mais peuvent Ć©galement ĆŖtre utilisĆ©s avec des articles optiques (
L'utilisation d'un tel revĆŖtement bicouche sur un article optique, tel qu'une lentille ophtalmique, permet de confĆ©rer Ć ladite lentille des propriĆ©tĆ©s polarisantes particuliĆØrement performantes. Il est ainsi possible d'obtenir des lentilles ophtalmiques prĆ©sentant un facteur de transmission relatif dans le visible (Tv) compris entre 80% et 6%, associĆ© Ć un rapport de contraste qui est supĆ©rieur Ć celui gĆ©nĆ©ralement observĆ© pour des lentilles polarisantes obtenues par collage ou laminage d'un film polarisant, et qui atteint couramment des valeurs supĆ©rieures Ć 100. Le revĆŖtement de type photopolymĆØre linĆ©aire (LPP) et de type polymĆØres cristaux liquides (LCP) peut ĆŖtre dĆ©posĆ© par centrifugation (spin) sur un substrat organique. Ce procĆ©dĆ© s'intĆØgre pleinement dans les chaĆ®nes de production et permet notamment l'obtention de lentille ophtalmique dont la lentille est constituĆ©e par tout type de substrat. Ce procĆ©dĆ© est particuliĆØrement bien adaptĆ© pour la rĆ©alisation de lentille comprenant un substrat Ć haut indice de rĆ©fraction (n = 1,6 - 1,67 ou 1,74), car ce procĆ©dĆ© n'altĆØre pas l'Ć©paisseur centre de la lentille, optimisation particuliĆØrement recherchĆ©e pour les matĆ©riaux Ć haut indice.The use of such a bilayer coating on an optical article, such as an ophthalmic lens, makes it possible to confer on said lens particularly effective polarizing properties. It is thus possible to obtain ophthalmic lenses having a relative relative transmission factor in the visible range (T v ) of between 80% and 6%, associated with a contrast ratio which is greater than that generally observed for polarizing lenses obtained by bonding or rolling a polarizing film, and which commonly reaches values greater than 100. The coating of linear photopolymer type (LPP) and liquid crystal polymer type (LCP) can be deposited by centrifugation (spin) on an organic substrate. This process is fully integrated into the production lines and allows in particular to obtain ophthalmic lens whose lens is constituted by any type of substrate. This method is particularly well suited for producing a lens comprising a substrate with a high refractive index (n = 1.6 - 1.67 or 1.74), since this method does not alter the center thickness of the lens. particularly sought after optimization for high index materials.
Comme indiquĆ© prĆ©cĆ©demment, les colorants dichroĆÆques prĆ©sents dans ces revĆŖtements polarisants bicouches sont sensibles aux UV, ce qui se traduit gĆ©nĆ©ralement par une perte des performances polarisantes, en particulier par une chute du rapport de contraste (CR), une augmentation de la transmission (Tv%) et un changement de teinte (ĪE), ce qui n'est pas acceptable pour une lentille polarisante qui doit ĆŖtre utilisable dans des conditions de fort ensoleillement.As indicated previously, the dichroic dyes present in these polarizing bilayer coatings are sensitive to UV, which generally results in a loss of polarizing performance, in particular by a drop in the contrast ratio (CR), an increase in transmission (Tv %) and a change in color (ĪE), which is not acceptable for a polarizing lens that must be usable under conditions of strong sunlight.
L'intĆ©gration directe d'absorbeurs UV au sein de la solution (LCP) (mĆ©langes de cristaux liquides, de colorants dichroĆÆques et de solvant(s)) avant polymĆ©risation de la couche risque d'empĆŖcher l'organisation des cristaux liquides et par consĆ©quent conduire Ć un mauvais alignement des colorants dichroĆÆques, ceci conduisant Ć de faible performances polarisantes. La protection efficace des colorants dichroĆÆques nĆ©cessiterait des proportions d'absorbeurs UV pour lesquelles la rĆ©alisation de ce risque deviendrait trĆØs probable.The direct integration of UV absorbers within the solution (LCP) (mixtures of liquid crystals, dichroic dyes and solvent (s)) before polymerization of the layer may prevent the organization of liquid crystals and consequently lead to misalignment of dichroic dyes, leading to poor polarizing performance. The effective protection of dichroic dyes would require proportions of UV absorbers for which the realization of this risk would become very likely.
Cette solution n'est donc pas compatible avec les prƩ requis.
Il est donc nĆ©cessaire de disposer d'un procĆ©dĆ© permettant l'introduction d'absorbeurs UV dans un article optique polarisĆ©, qui ne prĆ©sente pas les inconvĆ©nients mentionnĆ©s ci-dessus, et plus particuliĆØrement qui n'entraĆ®ne pas de modification des propriĆ©tĆ©s polarisantes du systĆØme et qui n'engendre pas de problĆØme d'adhĆ©rence avec d'Ć©ventuels autres revĆŖtements que l'article polarisĆ© pourrait contenir.This solution is therefore not compatible with the prerequisites.
It is therefore necessary to have a method allowing the introduction of UV absorbers in a polarized optical article, which does not have the drawbacks mentioned above, and more particularly which does not lead to a modification of the polarizing properties of the system. and which does not cause adhesion problems with any other coatings that the polarized article might contain.
Or, la Demanderesse a dƩcouvert que l'imbibition de l'article optique dans des conditions dƩterminƩes permettait de satisfaire ce besoin.Now, the Applicant has discovered that the imbibition of the optical article under specific conditions made it possible to satisfy this need.
La prƩsente invention a donc pour objet un procƩdƩ de fabrication d'un article optique polarisƩ, en particulier d'une lentille ophtalmique polarisƩe, comprenant au moins les Ʃtapes successives consistant respectivement :
- Ć appliquer, sur un substrat constitutif de l'article optique, un revĆŖtement polymĆ©risĆ© comprenant au moins un colorant sensible Ć la photodĆ©gradation, et
- Ć introduire un absorbeur UV dans ledit revĆŖtement,
- (a) le revĆŖtement polymĆ©risĆ© comprenant au moins un colorant sensible Ć la photodĆ©gradation est un revĆŖtement bicouche comprenant une premiĆØre couche de photopolymĆØres linĆ©aires (LPP) et une seconde couche de polymĆØres Ć cristaux liquides (LCP) comprenant au moins un colorant dichroĆÆque, et
- (b) l'absorbeur UV est introduit par imbibition au sein dudit revĆŖtement, ladite imbibition comprenant les Ć©tapes suivantes:
- (b1) immersion de l'article dans une solution aqueuse comprenant l'absorbeur UV et au moins un agent dispersant, pendant une durĆ©e comprise entre 10 secondes et 2 minutes, ladite solution Ć©tant maintenue Ć une tempĆ©rature comprise entre 80Ā°C et 99Ā°C, puis
- (b2) rinƧage de l'article par un alcool infƩrieur.
- applying, to a constituent substrate of the optical article, a polymerized coating comprising at least one dye sensitive to photodegradation, and
- introducing a UV absorber into said coating,
- (a) the polymerized coating comprising at least one photodegradation-sensitive dye is a bilayer coating comprising a first layer of linear photopolymers (LPP) and a second layer of liquid crystal polymers (LCP) comprising at least one dichroic dye, and
- (b) the UV absorber is introduced by imbibition within said coating, said imbibition comprising the following steps:
- (b1) immersing the article in an aqueous solution comprising the UV absorber and at least one dispersing agent for a period of between 10 seconds and 2 minutes, said solution being maintained at a temperature of between 80 Ā° C. and 99 Ā° C. C, then
- (b2) rinsing the article with a lower alcohol.
La prĆ©sente invention a Ć©galement pour objet un article optique polarisĆ© susceptible d'ĆŖtre obtenu selon le procĆ©dĆ© dĆ©fini prĆ©cĆ©demment.The present invention also relates to a polarized optical article that can be obtained according to the method defined above.
Elle a encore pour objet un article optique polarisƩ, en particulier une lentille ophtalmique polarisƩe, comprenant :
- un substrat,
- un revĆŖtement bicouche comprenant une premiĆØre couche de photopolymĆØres linĆ©aires (LPP) et une seconde couche de polymĆØres Ć cristaux liquides (LCP) renfermant au moins un colorant dichroĆÆque, et
- un absorbeur UV prĆ©sent au moins partiellement dans ledit revĆŖtement bicouche.
- a substrate,
- a bilayer coating comprising a first layer of linear photopolymers (LPP) and a second layer of liquid crystal polymers (LCP) containing at least one dichroic dye, and
- a UV absorber present at least partially in said bilayer coating.
Dans la prĆ©sente demande, les dĆ©finitions de certains termes doivent ĆŖtre comprises de la faƧon suivante :
- par article optique on entend les lentilles optiques d'instrumentation et de visĆ©e, les visiĆØres et les lentilles ophtalmiques,
- par lentille ophtalmique, on entend les lentilles s'adaptant notamment Ć une monture de lunette, ayant pour fonction de protĆ©ger l'oeil et/ou de corriger la vue, ces lentilles Ć©tant choisies parmi les lentilles afocales, unifocales, bifocales, trifocales et progressives,
- par substrat, on entend le matĆ©riau transparent constitutif de base de la lentille optique et plus particuliĆØrement de la lentille ophtalmique. Ce matĆ©riau sert de support Ć l'empilement d'un ou plusieurs revĆŖtements comprenant notamment les revĆŖtements polarisants,
- par revĆŖtement, on entend toute couche, film ou vernis pouvant ĆŖtre en contact avec le substrat, et/ou avec un autre revĆŖtement dĆ©posĆ© sur celui-ci, et pouvant notamment ĆŖtre choisi parmi les revĆŖtements teintĆ©s, anti-reflets, antisalissures, anti-chocs, anti-rayures, polarisants et antistatiques.
- optical article means optical lenses for instrumentation and sighting, visors and ophthalmic lenses,
- ophthalmic lens means the lenses adapting in particular to a spectacle frame, whose function is to protect the eye and / or to correct vision, these lenses being chosen from afocal, unifocal, bifocal, trifocal and progressive lenses ,
- "Substrate" means the basic constituent transparent material of the optical lens and more particularly of the ophthalmic lens. This material serves to support the stacking of one or more coatings including in particular polarizing coatings,
- coating means any layer, film or varnish that may be in contact with the substrate, and / or with another coating deposited thereon, and may in particular be selected from tinted coatings, anti-glare, antifouling, anti-shock, anti-scratch, polarizing and antistatic.
En outre, par Ā« alcool infĆ©rieur Ā», on entend un mono-alcool renfermant de 2 Ć 4 atomes de carbone tel que l'Ć©thanol ou l'isopropanol et en particulier l'isopropanol.
Le substrat de l'article optique, en particulier de la lentille ophtalmique, peut ĆŖtre de type minĆ©ral ou organique. A titre indicatif mais non limitatif, on peut citer comme substrat organique pouvant ĆŖtre utilisĆ© dans le cadre de l'invention les substrats classiquement utilisĆ©s en optique et en ophtalmie. Par exemple, sont adaptĆ©s les substrats du type polycarbonate; polyamide ; polyimides ; polysulfones ; copolymĆØres de poly(Ć©thylĆØnetĆ©rephtalate) et polycarbonate; polyolĆ©fines, notamment polynorbornĆØnes ; polymĆØres et copolymĆØres de diĆ©thylĆØneglycol bis(allylcarbonate); polymĆØres et copolymĆØres (mĆ©th)acryliques notamment polymĆØres et copolymĆØres (mĆ©th)acryliques dĆ©rivĆ©s de bisphenol-A; polymĆØres et copolymĆØres thio(mĆ©th)acryliques ; polymĆØres et copolymĆØres urĆ©thane et thiourĆ©thane ; polymĆØres et copolymĆØres Ć©poxy et polymĆØres et copolymĆØres Ć©pisulfide. D'une faƧon avantageuse, l'invention est particuliĆØrement bien adaptĆ©e pour les lentilles ophtalmiques dont le substrat est un poly(thio)urĆ©thane.In addition, "lower alcohol" means a mono-alcohol containing 2 to 4 carbon atoms such as ethanol or isopropanol and in particular isopropanol.
The substrate of the optical article, in particular of the ophthalmic lens, may be of mineral or organic type. As an indication but not limited to, there may be mentioned as an organic substrate that can be used in the context of the invention substrates conventionally used in optics and ophthalmia. For example, substrates of the polycarbonate type are suitable; polyamide; polyimides; polysulfones; copolymers of poly (ethylene terephthalate) and polycarbonate; polyolefins, especially polynorbornenes; polymers and copolymers of diethylene glycol bis (allyl carbonate); (meth) acrylic polymers and copolymers, especially polymers and (meth) acrylic copolymers derived from bisphenol-A; thio (meth) acrylic polymers and copolymers; urethane and thiourethane polymers and copolymers; epoxy polymers and copolymers and episulfide polymers and copolymers. Advantageously, the invention is particularly well suited for ophthalmic lenses whose substrate is a poly (thio) urethane.
La premiĆØre Ć©tape du procĆ©dĆ© selon l'invention comprend l'application du revĆŖtement bicouche. Ce revĆŖtement comprend une couche de photopolymĆØre(s) ou polymĆØre(s) photo-orientable(s) dĆ©posĆ©e sur le substrat et sur laquelle est dĆ©posĆ©e la couche de polymĆØre(s) Ć cristaux liquides.The first step of the process according to the invention comprises the application of the bilayer coating. This coating comprises a layer of photopolymer (s) or photo-orientable polymer (s) deposited on the substrate and on which the layer of polymer (s) liquid crystal is deposited.
L'application de ce revĆŖtement peut ĆŖtre effectuĆ©e suivant un procĆ©dĆ© comprenant les Ć©tapes gĆ©nĆ©rales successives consistant :
- 1- Ć prĆ©parer une solution d'au moins un photo-polymĆØre linĆ©aire,
- 2- Ć appliquer ladite solution sur le substrat, pour former une couche de photo-alignement,
- 3- Ć appliquer un rayonnement UV, en prĆ©sence d'un polariseur, Ć ladite couche de photo-alignement, de maniĆØre Ć la structurer,
- 4- Ć prĆ©parer une solution de cristaux liquides contenant au moins un colorant dichroĆÆque,
- 5- Ć appliquer ladite solution sur ladite couche de photo-alignement structurĆ©e,
- 6- Ć rĆ©ticuler la couche de cristaux liquides Ć l'aide d'une source de lumiĆØre UV.
- To prepare a solution of at least one linear photopolymer,
- 2- to apply said solution on the substrate, to form a photo-alignment layer,
- 3- to apply UV radiation, in the presence of a polarizer, to said photo-alignment layer, so as to structure it,
- 4- preparing a liquid crystal solution containing at least one dichroic dye,
- To apply said solution to said structured photo-alignment layer,
- 6- to crosslink the liquid crystal layer with a UV light source.
Les solutions de cristaux liquides et/ou de photo-polymĆØre linĆ©aire peuvent ĆŖtre appliquĆ©es par centrifugation (spin coating), trempage ou pulvĆ©risation. L'application par centrifugation est prĆ©fĆ©rĆ©e dans la prĆ©sente invention.Liquid crystal solutions and / or linear photopolymer can be applied by spin coating, dipping or spraying. Centrifugal application is preferred in the present invention.
Un revĆŖtement bicouche de ce type est notamment dĆ©crit dans la demande
La couche de photo-polymĆØre linĆ©aire peut ainsi ĆŖtre constituĆ©e de polymĆØres acryliques ou mĆ©thacryliques, de dendrimĆØres ou de polyimides, possĆ©dant des groupes rĆ©actifs du type dĆ©rivĆ©s d'acide cinnamique, chalcones ou coumarines. Ces matĆ©riaux peuvent ĆŖtre vĆ©hiculĆ©s dans un solvant tel que l'acĆ©tone, le dichloromĆ©thane, ou dans un mĆ©lange de solvant tel que mĆ©thylĆ©thylcĆ©tone/cyclopentanone. L'Ć©tape de photo-polymĆ©risation peut ĆŖtre rĆ©alisĆ©e aprĆØs une Ć©tape Ć©ventuelle de sĆ©chage de la solution, et ĆŖtre rĆ©alisĆ©e par exposition Ć la lumiĆØre UV polarisĆ©e.The linear photopolymer layer may thus consist of acrylic or methacrylic polymers, dendrimers or polyimides, having reactive groups of the cinnamic acid derivative type, chalcones or coumarins. These materials may be carried in a solvent such as acetone, dichloromethane, or in a solvent mixture such as methyl ethyl ketone / cyclopentanone. The photo-polymerization step can be carried out after a step possible drying of the solution, and be performed by exposure to polarized UV light.
Les polymĆØres Ć cristaux liquides et les colorants dichroĆÆques peuvent ĆŖtre vĆ©hiculĆ©s dans un solvant tel que cyclohexanone ou dans des mĆ©langes tels que anisole/acĆ©tone, anisole/acĆ©tate d'Ć©thyle ou anisole/cyclopentanone. Le revĆŖtement constituĆ© du mĆ©lange de cristaux liquides et de colorants dichroĆÆques peut ĆŖtre soumis (Ć©ventuellement aprĆØs une Ć©tape de sĆ©chage) Ć une irradiation UV afin de permettre sa polymĆ©risation.The liquid crystal polymers and the dichroic dyes may be carried in a solvent such as cyclohexanone or in mixtures such as anisole / acetone, anisole / ethyl acetate or anisole / cyclopentanone. The coating consisting of the mixture of liquid crystals and dichroic dyes may be subjected (possibly after a drying step) to UV irradiation to allow its polymerization.
Les colorants dichroĆÆques peuvent ou non ĆŖtre polymĆ©risables, de prĆ©fĆ©rence polymĆ©risables. Les colorants dichroĆÆques prĆ©fĆ©rĆ©s ont un rapport dichroĆÆque Ć©levĆ©, un coefficient d'extinction Ć©levĆ© et une bonne solubilitĆ©. Il peut s'agir de colorants azoĆÆques, perylĆØnes, anthraquinones ou phĆ©noxazines. Les colorants azoĆÆques et anthraquinones sont prĆ©fĆ©rĆ©s car particuliĆØrement bien compatibles avec les polymĆØres Ć cristaux liquides utilisĆ©s dans le cadre de l'invention.The dichroic dyes may or may not be polymerizable, preferably polymerizable. Preferred dichroic dyes have a high dichroic ratio, a high extinction coefficient, and good solubility. It can be azo dyes, perylenes, anthraquinones or phenoxazines. Azo and anthraquinone dyes are preferred because they are particularly well compatible with the liquid crystal polymers used in the context of the invention.
La Demanderesse a dĆ©montrĆ© que ce systĆØme polarisant, bien qu'ayant une faible tempĆ©rature de transition vitreuse une fois rĆ©ticulĆ© (Tg ā 20Ā°C), pouvait ĆŖtre imbibĆ© par une solution d'absorbeurs UV Ć une tempĆ©rature supĆ©rieure Ć 80Ā°C sans affecter notablement l'orientation des colorants dichroĆÆques. Ceci est aisĆ©ment mis en Ć©vidence par des mesures de contraste ratio avant et aprĆØs l'Ć©tape d'imbibition. Il est ainsi possible, avec ce systĆØme, d'utiliser des tempĆ©ratures d'imbibition Ć©levĆ©es, de l'ordre de 95Ā°C, qui permettent une diffusion rapide de l'absorbeur UV dans le systĆØme polarisant et donc l'obtention d'une coupure UV proche de 380 nm dĆØs 30 secondes d'imbibition. En outre, compte tenu de son caractĆØre rĆ©ticulĆ©, le systĆØme polarisant prĆ©citĆ© empĆŖche la dĆ©sorption de l'absorbeur UV lors du traitement ultĆ©rieur de l'article optique, par exemple lors de l'application d'un revĆŖtement anti-abrasion bicouche en prĆ©sence de soude et d'alcool, et confĆØre ainsi une bonne tenue chimique Ć l'article.
Le revĆŖtement ainsi obtenu a gĆ©nĆ©ralement une Ć©paisseur de 1 Ć 20 Āµm (micromĆØtre), et de prĆ©fĆ©rence de 3 Ć 8 Āµm.
La seconde Ć©tape du procĆ©dĆ© selon l'invention comprend l'imprĆ©gnation d'au moins un absorbeur UV dans l'article optique polarisĆ©.The Applicant has demonstrated that this polarizing system, although having a low glass transition temperature once crosslinked (Tg ā 20 Ā° C), could be imbibed by a UV absorber solution at a temperature above 80 Ā° C without affecting noticeably the orientation of the dichroic dyes. This is easily demonstrated by contrast ratio measurements before and after the imbibition step. It is thus possible, with this system, to use high imbibition temperatures, of the order of 95 Ā° C, which allow a rapid diffusion of the UV absorber in the polarizing system and thus obtaining a UV cut close to 380 nm after 30 seconds of imbibition. In addition, given its cross-linked nature, the aforementioned polarizing system prevents the desorption of the UV absorber during the subsequent treatment of the optical article, for example when applying a double-layer anti-abrasion coating in the presence of soda and alcohol, and thus confers a good chemical resistance to the article.
The coating thus obtained generally has a thickness of 1 to 20 microns (micrometer), and preferably 3 to 8 microns.
The second step of the process according to the invention comprises the impregnation of at least one UV absorber in the polarized optical article.
Des exemples non limitatifs d'absorbeurs UV utilisĆ©s dans le procĆ©dĆ© selon l'invention sont choisis parmi les benzotriazoles, en particulier l'hydroxyphĆ©nylbenzotriazole ; les triazines telles que l'hydroxyphĆ©nyl-S-triazine ; les hydroxy-benzophĆ©nones ; et les anilides oxaliques. L'absorbeur UV est prĆ©fĆ©rentiellement choisi parmi les absorbeurs de la famille des benzophĆ©nones et des benzotriazoles. Ces absorbeurs sont particuliĆØrement adaptĆ©s pour absorber les UV aux longueurs d'onde engendrant le plus de photodĆ©gradation des colorants sensibles aux UV, dans la plage intĆ©ressante dans le cadre de l'invention.Non-limiting examples of UV absorbers used in the process according to the invention are chosen from benzotriazoles, in particular hydroxyphenylbenzotriazole; triazines such as hydroxyphenyl-S-triazine; hydroxybenzophenones; and oxalic anilides. The UV absorber is preferably selected from the absorbers of the family of benzophenones and benzotriazoles. These absorbers are particularly suitable for absorbing UV at the wavelengths generating the most photodegradation of the UV-sensitive dyes, in the range of interest within the scope of the invention.
Les absorbeurs UV prĆ©fĆ©rentiellement choisis sont le CYASORBĀ® UV 24, le CYASORBĀ® UV-1164L, le CYASORBĀ® UV-1164 A, le CYASORBĀ® UV-2337, le CYASORBĀ® UV-531, le CYASORBĀ® UV-5411 et le CYASORBĀ® UV-9, tous disponibles dans le commerce auprĆØs de la sociĆ©tĆ© CYTEC.
D'autres absorbeurs UV utilisables dans la prĆ©sente invention sont l'UVINULĀ® 300, l'UVINULĀ® 3008, l'UVINULĀ® 3040, l'UVINULĀ® 3048, l'UVINULĀ® 3049 et l'UVINULĀ® 3050, disponibles auprĆØs de la sociĆ©tĆ© BASF.
D'autres exemples encore d'absorbeurs UV sont le TINUVINĀ® 1130, le TINUVINĀ® 292, le TINUVINĀ® 5151, le TINUVINĀ® 99-2, le TINUVINĀ® 384-2, le TINUVINĀ® 3050, le TINUVINĀ® 5055 et le TINUVINĀ® 5060 disponibles auprĆØs de la sociĆ©tĆ© CIBA.
D'autres exemples encore d'absorbeurs UV sont le SANDWORĀ® 3041, le le SANDUVORĀ® 3051, le SANDUVORĀ® 3063, le SANDUVORĀ® 3070 et le SANDUVORĀ® 3225 disponibles auprĆØs de la sociĆ©tĆ© CLARIANT.
Le CYASORBĀ® UV 24 est particuliĆØrement prĆ©fĆ©rĆ© dans la prĆ©sente invention ; il s'agit de la 2,2'-dihydroxy-4-mĆ©thoxybenzophenone.The preferably selected UV absorbers are the CYASORB Ā® UV 24, Cyasorb Ā® UV-1164L, Cyasorb Ā® UV-1164 A, CYASORB Ā® UV-2337, Cyasorb Ā® UV-531, Cyasorb Ā® UV-5411 and CYASORB Ā® UV-9, all commercially available from CYTEC.
Other UV absorbers used in the present invention are
Other examples of UV absorbers are TINUVIN Ā® 1130, TINUVIN Ā® 292, TINUVIN Ā® 5151, TINUVIN Ā® 99-2, TINUVIN Ā® 384-2, TINUVIN Ā® 3050, TINUVIN Ā® 5055 and TINUVIN Ā® 5060 available from CIBA.
Further examples of UV absorbers are SANDWOR Ā® 3041, the Sanduvor Ā® 3051, Sanduvor 3063 Ā®, 3070 Ā® Sanduvor and Sanduvor Ā® 3225 available from Clariant.
The CYASORB UV Ā® 24 is particularly preferred in the present invention; it is 2,2'-dihydroxy-4-methoxybenzophenone.
Au sein de la solution aqueuse d'imprĆ©gnation, un agent dispersant tel que l'acide dodĆ©cylbenzĆØnesulfonique est introduit. Cet agent dispersant permet d'Ć©viter la formation d'agrĆ©gat de l'absorbeur UV au sein de ladite solution d'imprĆ©gnation.In the aqueous impregnating solution, a dispersing agent such as dodecylbenzenesulphonic acid is introduced. This dispersing agent makes it possible to avoid the formation of aggregate of the UV absorber within said impregnation solution.
La quantitĆ© d'absorbeur UV au sein de la solution d'imprĆ©gnation doit ĆŖtre suffisamment importante pour permettre une imprĆ©gnation rapide du revĆŖtement polarisant prĆ©sent sur l'article optique, et suffisamment faible pour ne pas conduire Ć la formation d'agrĆ©gat au sein de la solution d'imprĆ©gnation. L'imprĆ©gnation rapide de l'article optique est une condition importante. En effet si le temps d'immersion de l'article optique est trop long (supĆ©rieur Ć 2 minutes) on constate un dĆ©collement du revĆŖtement de la surface du substrat constitutif de l'article optique.The amount of UV absorber in the impregnating solution must be large enough to allow rapid impregnation of the polarizing coating present on the optical article, and low enough not to lead to the formation of aggregate within the optical article. impregnation solution. The rapid impregnation of the optical article is an important condition. Indeed, if the immersion time of the optical article is too long (greater than 2 minutes) there is a detachment of the coating of the substrate surface constituting the optical article.
Le procĆ©dĆ© selon l'invention permet d'introduire l'absorbeur UV au moins partiellement dans le revĆŖtement bicouche polarisant.The method according to the invention makes it possible to introduce the UV absorber at least partially into the polarizing bilayer coating.
Pour ce faire, la durĆ©e d'immersion de l'article optique dans le bain d'immersion est comprise entre 10 secondes et 2 minutes. Il s'agit d'une durĆ©e optimale pour obtenir un article optique prĆ©sentant une rĆ©sistance Ć la photodĆ©gradation optimisĆ©e, tout en conservant de bonnes propriĆ©tĆ©s cosmĆ©tiques, un rapport de contraste similaire Ć celui obtenu pour un article polarisĆ© n'ayant pas subi le procĆ©dĆ© d'imprĆ©gnation, ainsi que de bonnes propriĆ©tĆ©s d'adhĆ©sion sur l'article optique tant de ladite bicouche que des Ć©ventuels revĆŖtements pouvant ĆŖtre dĆ©posĆ©s sur cette bicouche. Une durĆ©e d'immersion d'environ 30 secondes est particuliĆØrement prĆ©fĆ©rĆ©e.To do this, the immersion time of the optical article in the immersion bath is between 10 seconds and 2 minutes. This is an optimal time to obtain an optical article having optimized photodegradation resistance, while retaining good cosmetic properties, a contrast ratio similar to that obtained for a polarized article that has not undergone the process. impregnation, as well as good adhesion properties on the optical article of both said bilayer and any coatings that can be deposited on this bilayer. An immersion time of about 30 seconds is particularly preferred.
En outre, la tempĆ©rature du bain d'immersion, qui va de 80Ā°C Ć 99Ā°C, est de prĆ©fĆ©rence comprise entre 90Ā°C et 96Ā°C, plus prĆ©fĆ©rentiellement Ć©gale Ć 94Ā°C. Le bain d'immersion est une solution aqueuse.In addition, the temperature of the immersion bath, which ranges from 80 Ā° C to 99 Ā° C, is preferably between 90 Ā° C and 96 Ā° C, more preferably equal to 94 Ā° C. The immersion bath is an aqueous solution.
En plus du revĆŖtement polarisant prĆ©citĆ©, l'article optique fabriquĆ© selon l'invention pourra comprendre un ou plusieurs revĆŖtements tels que par exemple : un revĆŖtement anti-abrasion, par exemple de type bicouche, Ć©ventuellement appliquĆ© sur une couche de primaire ; un revĆŖtement teintĆ© ; un revĆŖtement formant barriĆØre contre l'oxygĆØne ; un revĆŖtement anti-reflet, par exemple Ć quatre couches ; un revĆŖtement anti-salissures hydrophobe et olĆ©ophobe ; ou un revĆŖtement antistatique. Un ou plusieurs de ces diffĆ©rents revĆŖtements peuvent ĆŖtre dĆ©posĆ©s directement sur le substrat avant dĆ©pĆ“t du revĆŖtement polarisant bicouche ou bien sur ledit revĆŖtement bicouche.In addition to the aforementioned polarizing coating, the optical article manufactured according to the invention may comprise one or more coatings such as for example: an anti-abrasion coating, for example of the bilayer type, optionally applied to a primer layer; a tinted coating; an oxygen barrier coating; an anti-reflective coating, for example four layers; a hydrophobic and oleophobic antifouling coating; or an antistatic coating. One or more of these different coatings may be deposited directly on the substrate before deposition of the bilayer polarizing coating or on said bilayer coating.
La couche de primaire, lorsqu'elle est utilisĆ©e, amĆ©liore la rĆ©sistance au choc de l'article sur laquelle elle est dĆ©posĆ©e et Ć©galement l'ancrage de la couche rĆ©sistant Ć l'abrasion. La couche de primaire peut ĆŖtre toute couche de primaire classiquement utilisĆ©e dans le domaine optique et en particulier ophtalmique. Typiquement, ces primaires, en particulier les primaires anti-choc, sont des revĆŖtements Ć base de polymĆØres (mĆ©th)acryliques, de polyurĆ©thanes, de polyesters, ou encore Ć base de copolymĆØres Ć©poxy/(mĆ©th)acrylate.The primer layer, when used, improves the impact strength of the article on which it is deposited and also the anchoring of the abrasion-resistant layer. The primer layer may be any primer layer conventionally used in the optical field and in particular ophthalmic. Typically, these primers, in particular the anti-shock primers, are coatings based on (meth) acrylic polymers, polyurethanes, polyesters, or based on epoxy / (meth) acrylate copolymers.
Le revĆŖtement anti-abrasion peut ĆŖtre tout revĆŖtement anti-abrasion classiquement utilisĆ© dans le domaine de l'optique et en particulier de l'optique ophtalmique. Par dĆ©finition, un revĆŖtement anti-abrasion est un revĆŖtement qui amĆ©liore la rĆ©sistance Ć l'abrasion de l'article d'optique fini comparĆ© au mĆŖme article ne comportant pas le revĆŖtement anti-abrasion.
Les revĆŖtements anti-abrasion prĆ©fĆ©rĆ©s sont ceux obtenus par durcissement d'une composition incluant un ou plusieurs Ć©poxyalcoxysilanes ou un hydrolysat de ceux-ci, de la silice et un catalyseur de durcissement. Des exemples de telles compositions sont dĆ©crits dans la demande internationale
Preferred anti-abrasion coatings are those obtained by curing a composition including one or more epoxyalkoxysilanes or a hydrolyzate thereof, silica and a curing catalyst. Examples of such compositions are described in the international application
Le revĆŖtement formant barriĆØre Ć l'oxygĆØne comprend gĆ©nĆ©ralement soit une couche d'oxyde mĆ©tallique dense, soit une couche d'oxyde mĆ©tallique non dense, soit un systĆØme comprenant un empilement de 1 Ć 4 couches d'oxydes mĆ©talliques diffĆ©rents.The oxygen barrier coating generally comprises either a dense metal oxide layer, a non-dense metal oxide layer, or a system comprising a stack of 1 to 4 different metal oxide layers.
Ce revĆŖtement peut ĆŖtre constituĆ© d'un film mono- ou multicouche, de matĆ©riaux tels que SiO, SiO2, Si3N4, TiO2, ZrO2, Al2O3, MgF2 ou Ta2O5, ou leurs mĆ©langes. D'une faƧon avantageuse, le systĆØme monocouche comprend du dioxyde de silicium, et prĆ©sente une Ć©paisseur comprise entre 10 et 100 nm. L'empilement comprend avantageusement une alternance d'au moins deux monocouches d'oxydes diffĆ©rents ces derniers Ć©tant avantageusement choisis parmi les oxydes de silicium, de titane, et de zirconium. L'empilement prĆ©sente avantageusement une Ć©paisseur comprise entre 50 nm et 300 nm, prĆ©fĆ©rentiellement entre 100 et 200 nm.
Ce revĆŖtement formant barriĆØre Ć l'oxygĆØne est appliquĆ© par des mĆ©thodes bien connues de l'homme du mĆ©tier, et gĆ©nĆ©ralement par dĆ©pĆ“t sous vide selon l'une des techniques suivantes :
- par Ʃvaporation, Ʃventuellement assistƩe par faisceau ionique;
- par pulvƩrisation par faisceau d'ions;
- par pulvƩrisation cathodique;
- par dƩpƓt chimique en phase vapeur assistƩe par plasma.
L'invention sera maintenant illustrƩe par l'exemple non limitatif suivant.
This oxygen barrier coating is applied by methods well known to those skilled in the art, and generally by vacuum deposition according to one of the following techniques:
- by evaporation, possibly assisted by ion beam;
- by ion beam sputtering;
- by sputtering;
- by plasma enhanced chemical vapor deposition.
The invention will now be illustrated by the following nonlimiting example.
Un revĆŖtement polarisant est appliquĆ© sur une lentille haut indice dont le substrat est un polythiourĆ©thane. Le polythiol prĆ©fĆ©rĆ© est le 1,2-bis(2'-mercaptoĆ©thylthio)-3-mercaptopropane (MDO). L'isocyanate prĆ©fĆ©rĆ© est le m-xylĆØnediisocyanate.
Le mode opƩratoire est tel que dƩcrit dans la demande de brevet
The procedure is as described in the patent application
La lentille est lavĆ©e dans une solution de soude Ć 5% dans un bain d'ultrasons Ć 55Ā°C. Elle est ensuite trempĆ©e dans de l'eau puis dans de l'eau dĆ©sionisĆ©e (Ć©ventuellement dans de l'isopropanol). Une solution Ć 2% en poids comprenant un polymĆØre acrylique prĆ©sentant des fonctions acides cinnamiques est prĆ©parĆ©e dans un mĆ©lange de mĆ©thylĆ©thylcĆ©tone et de cyclopentanone (10:1). Cette solution est dĆ©posĆ©e par centrifugation (spin) sur le substrat de la lentille. La vitesse de rotation est de 500 rpm pendant 3 secondes, puis de 2500 rpm pendant 20 secondes. Le solvant est Ć©vaporĆ© par chauffage dans une Ć©tuve Ć 100Ā°C pendant 20 minutes. Cette couche est irradiĆ©e sous un polariseur UV Ć une dose de 100 mJ/cm2.The lens is washed in a 5% sodium hydroxide solution in an ultrasound bath at 55 Ā° C. It is then soaked in water and then in deionized water (optionally in isopropanol). A 2% by weight solution comprising an acrylic polymer having cinnamic acid functions is prepared in a mixture of methyl ethyl ketone and cyclopentanone (10: 1). This solution is deposited by centrifugation (spin) on the substrate of the lens. The rotation speed is 500 rpm for 3 seconds, then 2500 rpm for 20 seconds. The solvent is evaporated by heating in an oven at 100 Ā° C for 20 minutes. This layer is irradiated under a UV polarizer at a dose of 100 mJ / cm 2 .
Une solution contenant des molĆ©cules de cristaux liquides et des colorants dichroĆÆques sensibles Ć la dĆ©gradation par les ultraviolets est prĆ©parĆ©e dans la cyclohexanone. La partie solide contenue dans cette solution est typiquement de 40% en poids. La quantitĆ© de colorant dichroĆÆque est d'environ 10% en poids. Cette solution est dĆ©posĆ©e par centrifugation sur la couche de LPP (vitesse de rotation = 500 rpm pendant 25 secondes). La couche de LCP est sĆ©chĆ©e pendant 10 minutes Ć une tempĆ©rature de 87Ā°C. AprĆØs Ć©vaporation des solvants, cette couche est rĆ©ticulĆ©e sous atmosphĆØre d'azote par irradiation en prĆ©sence d'une source UV Ć une dose de 30 J/cm2.A solution containing liquid crystal molecules and dichroic dyes sensitive to ultraviolet degradation is prepared in cyclohexanone. The solid part contained in this solution is typically 40% by weight. The amount of dichroic dye is about 10% by weight. This solution is deposited by centrifugation on the LPP layer (rotational speed = 500 rpm for 25 seconds). The LCP layer is dried for 10 minutes at a temperature of 87 Ā° C. After evaporation of the solvents, this layer is crosslinked under a nitrogen atmosphere by irradiation in the presence of a UV source at a dose of 30 J / cm 2 .
1500 ml d'eau distillĆ©e sont chauffĆ©s Ć 94Ā°C, sous agitation, dans un bĆ©cher en verre placĆ© sur un agitateur magnĆ©tique. Quand la tempĆ©rature atteint 90Ā°C, 3 g d'agent dispersant (l'acide dodĆ©cylbenzĆØnesulfonique) sont ajoutĆ©s et dispersĆ©s dans l'eau. Puis 13,05 g d'absorbeur UV CYASORB UV-24 sont ajoutĆ©s Ć la solution contenant l'agent dispersant. Le mĆ©lange est ensuite agitĆ© et chauffĆ© pendant environ 2 heures. La tempĆ©rature du bain est alors de 94Ā°C.1500 ml of distilled water are heated to 94 Ā° C, with stirring, in a glass beaker placed on a magnetic stirrer. When the temperature reaches 90 Ā° C, 3 g of dispersing agent (dodecylbenzenesulfonic acid) is added and dispersed in water. Then 13.05 g of CYASORB UV-24 UV absorber are added to the solution containing the dispersing agent. The mixture is then stirred and heated for about 2 hours. The temperature of the bath is then 94 Ā° C.
La lentille est plongĆ©e 30 secondes dans le bain prĆ©parĆ© comme dĆ©crit ci-dessus, avant d'ĆŖtre rincĆ©e dans un bain d'isopropanol afin d'Ć©liminer les rĆ©sidus d'acide et d'absorbeur UV prĆ©sents en surface de la lentille.The lens is immersed for 30 seconds in the bath prepared as described above, before being rinsed in an isopropanol bath in order to remove the acid and UV absorber residues present on the surface of the lens.
La coupure UV (Longueur d'onde pour laquelle la transmission devient infĆ©rieure Ć 1%) du revĆŖtement polarisĆ© seul est Ć©gale Ć 380 nm. Cette coupure UV est mesurĆ©e Ć l'aide d'un spectromĆØtre sur un revĆŖtement polarisĆ© dĆ©posĆ© sur un biplan minĆ©ral.The UV cutoff (wavelength for which the transmission becomes less than 1%) of the polarized coating alone is equal to 380 nm. This UV cutoff is measured using a spectrometer on a polarized coating deposited on a mineral biplane.
La
Un revĆŖtement bicouches anti-abrasion est appliquĆ© selon les Ć©tapes suivantes:
- premiĆØrement une couche de primaire latex est obtenue selon le protocole dĆ©crit dans l'exemple 1 du brevet
US 5,316,791 C pendant 4 minutes; l'Ć©paisseur de cette couche est de 1 Āµm ; - sur cette premiĆØre couche est dĆ©posĆ©e une couche obtenue selon le protocole dĆ©crit dans l'exemple 3 du brevet
EP 0 614 957
- firstly a latex primer layer is obtained according to the protocol described in example 1 of the patent
US5,316,791 step 2 and is heated at 87 Ā° C for 4 minutes; the thickness of this layer is 1 Ī¼m; - on this first layer is deposited a layer obtained according to the protocol described in Example 3 of the
patent EP 0 614 957
Un revĆŖtement anti-reflet traditionnel Ć quatre couches, comprenant une alternance de couches d'oxydes de zirconium et de silicium est ensuite appliquĆ© jusqu'Ć atteindre une Ć©paisseur totale d'empilement de 200 nm.A traditional four-layer anti-reflective coating comprising alternating zirconium oxide and silicon oxide layers is then applied until a total stacking thickness of 200 nm is achieved.
Les diffƩrentes couches sont rƩalisƩes dans une machine BAK, en rotation sous un vide poussƩ de 2 x 10-5.The different layers are made in a BAK machine, rotating under a high vacuum of 2 x 10 -5 .
On a comparĆ© par des essais de vieillissement accĆ©lĆ©rĆ© effectuĆ©s Ć l'aide d'un Suntest les configurations suivantes :The following configurations were compared by accelerated aging tests carried out using a Suntest:
Le principe de ce test est dƩcrit ci-dessous :
- Les verres sont placĆ©s dans l'Ć©quipement Suntest qui produit un Ć©clairement de 60 klux. Ils subissent des cycles successifs de vieillissement solaire de 50 heures. La durĆ©e totale d'exposition varie de 50 Ć 200 heures. A l'issue de chaque cycle d'Ć©clairement, une ou plusieurs caractĆ©ristiques optiques du produit sont mesurĆ©es pour dĆ©terminer une Ć©ventuelle Ć©volution. Il s'agit principalement de la transmission visuelle (Tv), du rapport de contraste (CR) et de la dĆ©termination des paramĆØtres colorimĆ©triques (L*, a*, b*).
- Pour chacune des configurations, on a mesurĆ© la transmission (Tv), le rapport de contraste (CR) et l'Ć©cart colorimĆ©trique (ĪE = (ĪL2+Īa2+Īb2)1/2).
- Les rƩsultats sont rassemblƩs dans les Tableaux 1
et 2 suivants :
- The lenses are placed in the Suntest equipment which produces an illuminance of 60 klux. They undergo successive cycles of solar aging of 50 hours. The total duration of exposure ranges from 50 to 200 hours. At the end of each illumination cycle, one or more optical characteristics of the product are measured to determine a possible evolution. These are mainly the visual transmission (Tv), the contrast ratio (CR) and the determination of the colorimetric parameters (L *, a *, b *).
- For each of the configurations, the transmission (Tv), the contrast ratio (CR) and the color difference (ĪE = (ĪL 2 + Īa 2 + Īb 2 ) 1/2) were measured.
- The results are summarized in the following Tables 1 and 2:
Comme il ressort de ces tableaux, l'imbibition de la lentille entraĆ®ne une moindre diminution de l'efficacitĆ© de polarisation, mesurĆ©e par le rapport de contraste CR aprĆØs 50h au Suntest. Surtout, le changement de coloration ĪE des lentilles est moindre et la transmission Tv augmente nettement moins.As can be seen from these tables, imbibition of the lens results in a smaller decrease in polarization efficiency, as measured by the CR contrast ratio after 50 hours at Suntest. Above all, the color change ĪE of the lenses is less and the transmission Tv increases significantly less.
Les
Claims (12)
- A method of manufacturing a polarized optical article, in particular a polarized ophthalmic lens, comprising at least the following successive steps of :applying, to a substrate of the optical article, a polymerized coating comprising at least one dye that is sensitive to photodegradation; andintroducing a UV absorber into said coating;characterized by the fact that(a) the polymerized coating comprising at least one dye that is sensitive to photodegradation is a bilayer coating comprising a first layer of linear photopolymers (LPP) and a second layer of liquid crystal polymers (LCP) comprising at least one dichroic dye; and(b) the UV absorber is introduced into said coating by imbibition, said imbibition comprising the following steps:(b1) immersion of the article in an aqueous solution comprising the UV absorber and at least one dispersing agent, for a period of time of between 10 seconds and 2 minutes, said solution being kept at a temperature of between 80Ā°C and 99Ā°C; then(b2) rinsing of the article with a lower alcohol.
- The method according to Claim 1, characterized by the fact that said substrate is selected from the group consisting of polycarbonate; polyamide; polyimides; polysulphones; poly(ethylene terephthalate) / polycarbonate copolymers; polyolefins, especially polynorbornenes; diethylene glycol bis(allylcarbonate) polymers and copolymers; (meth)acrylic polymers and copolymers, especially (meth)acrylic polymers derived from bisphenol A; thio(meth)acrylic polymers and copolymers; urethane and thiourethane polymers and copolymers; epoxy polymers and copolymers and episulphide polymers and copolymers.
- The method according to Claim 2, wherein the substrate is a poly(thio)urethane.
- The method according to any of claims 1 to 3, characterized by the fact that the application of the bilayer coating is carried out according to a method comprising the following successive steps .1- preparing a solution of at least one linear photopolymer;2- applying said solution to the substrate, in order to form a photoalignment layer;3- applying UV radiation, in the presence of a polarizer, to said photoalignment layer, so as to structure it;4- preparing a liquid crystal solution containing at least one dichroic dye;5- applying said solution to said structured photoalignment layer;6- crosslinking the liquid crystal layer using a UV light source.
- The method according to any of claims 1 to 4, characterized by the fact that said UV absorber is selected from the group consisting of benzotriazoles, especially hydroxyphenylbenzotriazole; triazines such as hydroxyphenyl-S-triazine; hydroxybenzophenones; and oxalic anilides.
- The method according to Claim 5, characterized by the fact that said UV absorber is 2,2'-dihydroxy-4-methoxybenzophenone.
- The method according to any of claims 1 to 6, characterized by the fact that the dispersing agent is dodecylbenzenesulphonic acid.
- The method according to any of claims 1 to 7, characterized by the fact that the immersion time of the optical article in the solution containing the UV absorber is about 30 seconds.
- The method according to any of claims 1 to 8, characterized by the fact that the temperature of the immersion bath is between 90Ā°C and 96Ā°C.
- The method according to Claim 9, characterized by the fact that the temperature of the immersion bath is equal to 94Ā°C.
- The method according to any of claims 1 to 10, characterized by the fact that the optical article further comprises one or more coatings selected from the group consisting of an abrasion-resistant coating, for example a bilayer coating optionally applied to a primer layer; a tinted coating; an oxygen barrier coating; an anti-reflection coating; a hydrophobic and oleophobic anti-soiling coating; and an anti-static coating.
- An optical article obtainable according to the method defined in any one of Claims 1 to 11.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0512277A FR2894340B1 (en) | 2005-12-02 | 2005-12-02 | METHOD FOR MANUFACTURING OPTICAL ARTICLE AND ARTICLE THUS OBTAINED |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1798272A1 EP1798272A1 (en) | 2007-06-20 |
| EP1798272B1 true EP1798272B1 (en) | 2011-12-14 |
Family
ID=36910954
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP06291705A Not-in-force EP1798272B1 (en) | 2005-12-02 | 2006-11-03 | Manufacturing process for an optical article and article so obtained |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20070126983A1 (en) |
| EP (1) | EP1798272B1 (en) |
| JP (1) | JP2007156464A (en) |
| AT (1) | ATE537239T1 (en) |
| FR (1) | FR2894340B1 (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2897694B1 (en) * | 2006-02-23 | 2008-05-16 | Essilor Int | METHOD FOR PRODUCING A POLARIZING OPTICAL ELEMENT |
| JP5714920B2 (en) * | 2010-01-21 | 2015-05-07 | Hoyaę Ŗå¼ä¼ē¤¾ | Manufacturing method of polarizing member |
| CN102782565A (en) * | 2010-01-22 | 2012-11-14 | å„„å å©ęéå ¬åø | Lenses for 3D eyewear |
| WO2012078197A1 (en) * | 2010-01-22 | 2012-06-14 | Oakley, Inc. | Eyewear with three-dimensional viewing capability |
| US8770749B2 (en) | 2010-04-15 | 2014-07-08 | Oakley, Inc. | Eyewear with chroma enhancement |
| JP5568800B2 (en) | 2010-09-08 | 2014-08-13 | ę„ę±é»å·„ę Ŗå¼ä¼ē¤¾ | Method for producing water-resistant optically anisotropic film and image display device |
| JP2013054275A (en) * | 2011-09-06 | 2013-03-21 | Nikon-Essilor Co Ltd | Dyed lens and method of manufacturing the same |
| WO2013070417A1 (en) | 2011-10-20 | 2013-05-16 | Oakley, Inc. | Eyewear with chroma enhancement |
| JP5887660B2 (en) | 2011-12-07 | 2016-03-16 | ę„ę±é»å·„ę Ŗå¼ä¼ē¤¾ | Method for producing water-resistant optically anisotropic film |
| WO2013169987A1 (en) | 2012-05-10 | 2013-11-14 | Oakley, Inc. | Eyewear with laminated functional layers |
| US9575335B1 (en) | 2014-01-10 | 2017-02-21 | Oakley, Inc. | Eyewear with chroma enhancement for specific activities |
| US10871661B2 (en) | 2014-05-23 | 2020-12-22 | Oakley, Inc. | Eyewear and lenses with multiple molded lens components |
| WO2016077431A2 (en) | 2014-11-13 | 2016-05-19 | Oakley, Inc. | Variable light attenuation eyewear with color enhancement |
| US9905022B1 (en) | 2015-01-16 | 2018-02-27 | Oakley, Inc. | Electronic display for demonstrating eyewear functionality |
| US12124116B2 (en) | 2017-10-20 | 2024-10-22 | Luxottica S.R.L. | Eyewear with variable transmission lens |
| US11112622B2 (en) | 2018-02-01 | 2021-09-07 | Luxottica S.R.L. | Eyewear and lenses with multiple molded lens components |
| EP3542956A1 (en) | 2018-03-23 | 2019-09-25 | Carl Zeiss Vision International GmbH | Method for manufacturing spectacle lenses according to a prescription |
| CN113835141A (en) * | 2021-11-08 | 2021-12-24 | å¦éØč°Øå¾·å ēµē§ęęéå ¬åø | Fade-proof ultraviolet-resistant sunglasses lens |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01163703A (en) * | 1987-09-30 | 1989-06-28 | Hoya Corp | Plastic lens |
| DE3904371A1 (en) * | 1989-02-14 | 1990-08-16 | Basf Ag | METHOD FOR PRODUCING 2,4-DIHYDROXYBENZOPHENONE |
| JP2503068B2 (en) * | 1989-02-22 | 1996-06-05 | ćć¼ć¤ę Ŗå¼ä¼ē¤¾ | Eyeglass lenses for lens extractors |
| JP2813390B2 (en) * | 1989-10-30 | 1998-10-22 | ćć¼ć¤ę Ŗå¼ä¼ē¤¾ | Eyeglass lens for lensectomy |
| US5976638A (en) * | 1993-01-26 | 1999-11-02 | Akzo Nobel Nv | Optical recording medium comprising a homeotropically oriented liquid crystalline polymer film comprising dichroic dye |
| JP3898776B2 (en) * | 1995-11-20 | 2007-03-28 | ćć³ćæććÆć¹ę Ŗå¼ä¼ē¤¾ | Lens staining method |
| US5738803A (en) * | 1995-12-14 | 1998-04-14 | Hoechst Celanese Corp | Polarizer films comprising wholly aromatic liquid crystalline polymers and dichroic dyes |
| JPH1152101A (en) * | 1997-08-01 | 1999-02-26 | Seiko Epson Corp | Plastic lens manufacturing method |
| CA2246505A1 (en) * | 1998-09-03 | 2000-03-03 | Christophe U. Ryser | Method for tinting tint-able plastic material using microwave energy |
| EP1381910A1 (en) * | 2001-04-24 | 2004-01-21 | MERCK PATENT GmbH | Liquid crystal device exhibiting optical properties which are changeable after assembly |
| EP1462485A1 (en) * | 2003-03-26 | 2004-09-29 | Rolic AG | Polymerizable dichroic azo dyes |
| EP1593990B1 (en) * | 2004-05-07 | 2007-12-05 | ESSILOR INTERNATIONAL (Compagnie GƩnƩrale d'Optique) | Polarizing and abrasion-resistant optical film and process for manufacturing thereof |
-
2005
- 2005-12-02 FR FR0512277A patent/FR2894340B1/en not_active Expired - Fee Related
-
2006
- 2006-11-03 EP EP06291705A patent/EP1798272B1/en not_active Not-in-force
- 2006-11-03 AT AT06291705T patent/ATE537239T1/en active
- 2006-11-27 JP JP2006318191A patent/JP2007156464A/en active Pending
- 2006-11-30 US US11/606,427 patent/US20070126983A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| US20070126983A1 (en) | 2007-06-07 |
| FR2894340A1 (en) | 2007-06-08 |
| FR2894340B1 (en) | 2008-02-15 |
| JP2007156464A (en) | 2007-06-21 |
| EP1798272A1 (en) | 2007-06-20 |
| ATE537239T1 (en) | 2011-12-15 |
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